Method and compositions for reducing wear in engines combusting ethanol-containing fuels

ABSTRACT

The present disclosure provides a method to reduce wear and prevent deposit formation in an internal combustion engine, said method comprising combusting in said engine a fuel composition comprising gasoline, ethanol and at least one fuel additive. There is also provided a composition to improve wear protection in an internal combustion engine combusting an ethanol-containing fuel, said composition comprising gasoline, ethanol, and one or more fuel additive materials.

FIELD

The present disclosure relates to the use of fuel additives in fuelscontaining ethanol. The additives improve the properties of theresulting fuel and also enhance the benefits to the consumer and to theenvironment of utilizing varying amounts of ethanol as a fuel incombustion engines. More particularly, the present disclosure providescompositions and methods for reducing engine deposits and improvingengine wear in engines combusting ethanol-containing gasoline fuelblends.

BACKGROUND

Much has been said about the use of ethanol as a fuel by itself, andalso as a blend component for use with gasoline, and even with dieselfuels. Ethanol can be produced from crops and thus provides a viablerenewable fuel source.

A common blend of gasoline and ethanol being discussed is 15% gasolineand 85% ethanol, often commonly referred to as “E85” fuel (hereinafter“E85”). Other ethanol fuels can comprise, for example 10% ethanol (E10)and 100% ethanol (E100).

The use of ethanol alone or in gasoline blends can create new problemsfor fuel equipment designed to handle the more non-polarhydrocarbonaceous petroleum fractions commonly known as gasolines. Thepolarity, corrosivity, adhesiveness, friction properties, and perhapsconductivity of ethanol or ethanol-containing fuel can create newproblems and new needs in the fuel industry.

E85, gasoline, and diesel are seasonally adjusted to ensure properstarting and performance in different geographic locations. For example,E85 sold during colder months often contain only 70% ethanol and then30% petroleum additives to produce the necessary vapor pressure forstarting in cold temperatures. During warmer months the petroleumadditive content for E85 can often be, for example, 17% to about 20%.However, as the interest increases to other fuel blends and to possiblywider use of E100, the need for better cold start performance andreliability will increase.

So-called “driveability” of a vehicle is a function of the fuelcombustion performance and poor driveability is manifested as slowstarts, uneven combustion, and potential for misfires and stalling.Various techniques and fuel additives have been employed in the past toaddress this problem with gasoline fuels. Ethanol-containing fuels, fromE100 to E5, and other gasoline-ethanol blends will produce additionalproblems with achieving improved driveability. A need exists to improvethe driveability of vehicles combusting such gasoline-ethanol blends.

Similarly, engine wear can be a problem in engines combusting ethanol orethanol-containing gasoline fuels, particularly in older enginesdesigned and built before the introduction of ethanol-containing fuels.This engine wear can appear as corrosion or increased deposits. And willoften result in decreased driveability, reduced fuel economy, or evencatastrophic engine failure. A need exists for a method and fuelcompositions to reduce the engine wear in engines combustingethanol-containing fuels, such as gasoline.

Commercial ethanol is widely treated with additives designed to preventhuman consumption. Such treated ethanol is called denatured alcohol, ordenatured ethanol and common denaturants include gasoline, gasolinecomponents, and kerosene. Other denaturants for rendering fuel alcoholunfit for beverage use are defined in 27 CFR 21.24.

Fuel delivery systems in vehicles combusting gasoline fuels haveincreasingly complicated componentry, some of which is, can be or willbe highly sensitive to variations in certain fuel parameters. Physicaland chemical properties of the fuel can negatively impact theperformance or life of these fuel delivery systems. Thus, certaincomponents designed for use in traditional gasolines might besusceptible to fatigue, reduce performance or complete failure uponprolonged exposure to fuels containing ethanol, particularly fuelscontaining high percentages of ethanol, like E85 and E100. Therefore, aneed exists to protect such older engines and well as improve thereliability of newer engines when all are exposed to prolongedcombustion of ethanol-containing fuels.

The use of varying degrees of ethanol in gasoline fuels can createproblems with, for example, increased engine deposits, fuel stability,corrosion, fuel economy, fuel driveability, luminosity, fuel economy,fuel driveability, luminosity, fuel economy, demulse, ignition,driveability, driveability, antioxidancy, oil drain interval, achievingCARB standards, achieving Top-Tier auto-maker standards, achieving USEPA standards, solubility, component compatibility, fuel line plugging,engine durability, engine ear, and injector fouling, which will benefitfrom the inclusion in the fuel of certain fuel additives.

As currently offered to consumers by several automakers, flexible fuelvehicles (FFVs) are designed to operate on any mixture of gasoline andethanol—with ethanol concentrations of up to 85% by volume (E85). Thereis one major difference between an FFV and a conventionalgasoline-fueled vehicle—the FFV detects the ethanol/gasoline ratio andmakes appropriate adjustments to the engine's ignition timing andair/fuel mixture ratios to account for the ethanol and optimizeperformance and maintain emissions control. The vehicle must be equippedwith an air/fuel ratio map capable of handling the adjustments necessaryfor optimized performance on both gasoline and E85. Components of thefuel delivery systems on FFVs are also modified and upgraded to beresistant to the corrosive effects of alcohol in the fuel.

Much like gasoline, the volatility of E85 must be adjusted seasonallyand by geographic region to assure adequate cold start and drive awayperformance. This is done by increasing the amount of gasoline(typically from 15% to 30% by volume) in blends sold during coldermonths.

Pure ethanol has broader flammability limits than gasoline and burnswith lower flame luminosity. When blended with hydrocarbon fuels, thevapor space flammability limits of ethanol approach those of gasolineand luminosity is increased.

OGA-480, a polyetheramine available from Chevron Oronite, has been usedin E100 fuel but has not been used in E85, nor have other amines beenused in ethanol/gasoline blends, to the knowledge of the presentinventors.

SUMMARY OF THE EMBODIMENTS

An embodiment presented herein provides fuel additive agents for use inreducing wear and deposits in engines combusting ethanol-containingfuels, including but not limited to E100, E85, E50, and the like down toE10 and trace blends of ethanol in gasoline.

Another embodiment provides a method to reduce wear and/or depositformation in an internal combustion engine, said method comprisingcombusting in said engine a fuel composition comprising gasoline,ethanol and at least one fuel additive.

Accordingly, in one example herein is provided a composition to improvewear protection and/or to reduce deposit formation in an internalcombustion engine combusting an ethanol-containing fuel, saidcomposition comprising gasoline, ethanol, and one or more materialsselected from the group consisting of succinimide dispersants,succinamide dispersants, amides, Mannich base dispersants,polyetheramine dispersants, p-phenylenediamine, dicyclohexylaminephenolics, hindered phenolics, aryl amines, diphenyl amines,monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methylcyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganesetricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolicresins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol,methyloxirane and oxirane, octane enhancer materials, monoesters,diesters, ethers, diethers, methyloxirane, oxiranes, peroxides, alkylnitrates, C1-C8 aliphatic hydrocarbons (such as alkanes), ketones,butylene oxides, propylene oxides, ethylene oxides, epoxides, butane,pentane, nitrous oxide, nitromethane, xylene, diethyl ether, polyethers,glycols, phenates, salicylates, sulfonates, nonylphenol ethoxylates,alkali detergents and an alkaline earth metal-containing detergents.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are intended to provide further explanation of the presentdisclosure, as claimed.

DETAILED DESCRIPTION OF EMBODIMENTS

By “ethanol” herein is meant ethyl alcohol, the chemical compoundC₂H₅OH. This can arise in or be provided in many qualities or grades,such a commercial of fuel grade, as well as pure or reagent gradeethanol, and can be derived from any source such as but not limited topetroleum refinery streams, distillation cuts, and bio-derived (e.g.bioethanol from corn).

Fuels containing varying amounts of ethanol can, when evaporated orcombusted, produce increased engine wear as well as increased enginedeposits relative to deposits produced from evaporation or combustion ofgasoline alone. By the present disclosure the engine wear and depositscan be reduced or prevented by combusting a fuel composition containingthe gasoline, ethanol and one or more fuel additive as described herein.

By the present disclosure is provided in one embodiment a method toreduce wear and/or deposits in an internal combustion engine combustingan ethanol-containing fuel, said method comprising combusting in saidengine a fuel containing gasoline, ethanol, and one or more wearreducing agents selected from the group consisting of succinimidedispersants, succinamide dispersants, amides, Mannich base dispersants,polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine,phenolics, hindered phenolics, aryl amines, diphenyl amines,monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methylcyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganesetricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolicresins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol,methyloxirane and oxirane, octane enhancer materials, monoesters,diesters, ethers, diethers, methyloxirane, oxiranes, peroxides, alkylnitrates, C1-C8 aliphatic hydrocarbons (such as alkanes), ketones,butylene oxides, propylene oxides, ethylene oxides, epoxides, butane,pentane, nitrous oxide, nitromethane, xylene, diethyl ether, polyethers,glycols, phenates, salicylates, sulfonates, nonylphenol ethoxylates,alkali detergents and an alkaline earth metal-containing detergents.

The compositions herein can further comprise a fuel additive selectedfrom the group consisting of lubricity additives, combustion improvers,detergents, dispersants, cold flow improvers, dehazers, demulsifiers,cetane improvers, antioxidants, scavengers, and pollution suppressants.

Also provided herein is a deposit reducer fuel additive concentrate forgasoline engines combusting an ethanol-containing fuel, said concentratecomprising one or more deposit reducing agents and a diluent selectedfrom the group consisting of an oil, a fuel, gasoline, ethanol, solvent,carrier fluid, and other liquid materials combustible in a gasolineengine.

Further provided herein is a wear reducer fuel additive concentrate forgasoline engines combusting an ethanol-containing fuel, said concentratecomprising one or more wear reducing agents and a diluent selected fromthe group consisting of an oil, a fuel, gasoline, ethanol, solvent,carrier fluid, and other liquid materials combustible in a gasolineengine.

In another embodiment the wear or deposit reducer is selected from thegroup consisting of methyloxirane, oxiranes, peroxides, alkyl nitrates,C1-C8 aliphatic hydrocarbons, ketones, butylene oxides, propyleneoxides, ethylene oxides, epoxides, butane, pentane, nitrous oxide,nitromethane, xylene, and diethyl ether.

Particularly useful wear and/or deposit reducers herein are tall oilfatty acids, dodecenyl succinic acid, and oleic acid plus N,Ndimethylcyclohexylamine.

Also provided herein is a method to reduce deposit formation in aninternal combustion engine combusting an ethanol-containing fuel, saidmethod comprising, or in another embodiment, consisting essentially of,combusting in said engine a fuel containing gasoline, ethanol, and oneor more materials selected from the group consisting of succinimidedispersants, succinamide dispersants, amides, Mannich base dispersants,polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine,phenolics, hindered phenolics, aryl amines, diphenyl amines,monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methylcyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganesetricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolicresins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol,methyloxirane and oxirane, octane enhancer materials, monoesters,diesters, ethers, methyloxirane, oxiranes, peroxides, alkyl nitrates,C1-C8 aliphatic hydrocarbons, ketones, butylene oxides, propyleneoxides, ethylene oxides, epoxides, butane, pentane, nitrous oxide,nitromethane, xylene, diethyl ether, diethers, polyethers, glycols,phenates, salicylates, sulfonates, nonylphenol ethoxylates, alkalidetergents and an alkaline earth metal-containing detergents.

Vapor Pressure Ethanol Blend at 77 F. mmHg E100 59.02 E75 250.60 +4%pentane 256.60 +8% pentane 262.60 +10% pentane 265.60 E85 188.14 +0.1%Pentane 188.25 +0.5% Pentane 188.68 +1% Pentane 189.23 +4% Pentane192.47 +8% Pentane 196.77 +10% Pentane 198.90 +0.1% Butane 188.87 +0.5%Butane 191.77 +1% Butane 195.38 +4% Butane 217.00 +8% Butane 245.70 +10%Butane 260.00 +4% diethyl ether 188.05 +8% diethyl ether 187.95 +10%diethyl ether 187.89 +0.1% dimethyl ether 189.13 +0.5% dimethyl ether193.07 +1% dimethyl ether 197.99 +4% dimethyl ether 227.40 +8% dimethylether 266.30 +10% dimethyl ether 285.70

EXAMPLES

TABLE 1 IVD Rig Test Deposits From E85 Fuels Ethanol Source Deposit, mg.New Energy Ethanol 1.6 ADM Ethanol 10.8 New Energy Ethanol is acommercial ethanol with a denaturant ADM Ethanol is ethanol with acorrosion inhibitor (DCI-11, from Innospec) and a denaturant

Table 1 shows the intake valve deposits generated on an Intake ValveDeposit simulator rig test using E85 fuels containing the ethanolsindicated. In this rig test, the fuel blend is sprayed onto a hotsurface and the resulting residue weighed. The base gasoline was CitgoRUL and without any additives the Intake Valve Deposit rating for thebase gasoline in the rig test was 12.4 mg. As can be seen, the twodifferent ethanol sources (New Energy and ADM) yielded significantdifferences, indicating a need for additives and a problem ofnon-uniformity across ethanol suppliers. While both ethanol productscontain a denaturant, the ADM Ethanol is further believed to have 32 PTBof a corrosion inhibitor known commercially as DCI-11 from Innospec. Ascan be seen by comparing the rig test deposits from these two ethanolswhen used in E85 gasoline-ethanol fuel blend, the ADM Ethanol generateda 10-fold increase in deposits relative to the deposits produced by theNew Energy Ethanol in the rig test. Such an E85 fuel will therefore needmore detergents, dispersants and other additives than E85 fuelsutilizing other ethanol sources.

TABLE 2 IVD Rig Test Deposits on E85 Fuel Containing Additives Dosage,Additive in ptb Deposit, mg H-4733 10 1.4 H-3000 25 0.9 H-4142 50 1.0H-4848A 50 12.7 H-4247 38 15.6 DDSA 50% 25 0.5 H-6560 100 4.0 AP-5000100 2.1 H-4705 20 1.5 GAR515A01 100 2.7 H-6457 50 2.7 H-4858 50 18.9H-6400 100 6.6 H-4103 5000 ppmv 0.4 H-4733 is 2,6-di t-butyl phenolantioxidant H-3000 is methylcyclopentadienyl manganese tricarbonylH-4142 is oleic acid plus N,N dimethylcyclohexylamine H-4848A isdiethanol amide, demulsifier, aromatic solvent H-4247 is succinimidedispersant and aromatic solvent DDSA 50% is dodecenyl succinic acid inA150 solvent H-6560 is Mannich base dispersant from dibutyl amineAP-5000 is BASF polyisobutylene amine dispersant H-4705 is 1,2 propanediamine salicylaldehyde metal deactivator GAR515A01 is a cresol Mannichdispersant from dibutyl amine; and polyol H-6457 is diethanol amide ofisostearic acid friction modifier H-4858 is ethylene glycol ester-basedlubricity additive H-6400 is polyetheramine and DDS corrosion inhibitor,Tolad demulsifier, aromatic solvent H-4103 is 2-ethyl hexyl nitratecombustion improver Ptb is pounds per thousand barrelsTable 1 shows the intake valve deposits generated on the Intake ValveDeposit simulator rig test using E85 fuels containing the New EnergyEthanol. The dosage reported is the treat rate of the additive in thegasoline-ethanol fuel blend. As can be seen by comparing the rig testdeposits from these additives when used in the E85 gasoline-ethanol fuelblend, the deposits varied. However, it must be noted that (a) thistable used the ethanol contributing the lowest deposit level (New EnergyEthanol), so other ethanol sources, such as ADM Ethanol, will clearlyhave significantly more need for detergents, dispersants and other fueladditives, and (b) the deposits shown in Table 2 will include about 1.6mg of deposits from the New Energy Ethanol in the E85 fuel. Thus, for atleast those additives that generated deposits of about 2.7 mg or less,the total effective deposit not coming from the ethanol is essentiallyzero, that is, the present disclosure shows in at least theseembodiments virtually complete prevention of deposits and the resultingwear on the engine. These additives include 2,6-di t-butyl phenolantioxidant, methylcyclopentadienyl manganese tricarbonyl combustionimprover and octane enhancer, oleic acid plus N,Ndimethylcyclohexylamine, dodecenyl succinic acid, polyisobutylene aminedispersant, 1,2 propane diamine salicylaldehyde metal deactivator,cresol Mannich dispersant, diethanol amide of isostearic acid frictionmodifier, and 2-ethyl hexyl nitrate combustion improver. The alkylnitrate, 2-ethyl hexyl nitrate, was particularly effective in reducingdeposits and hence improving wear in the engine combusting the E85 fuelblend.

Thus, there is provided herein a method of reducing deposits formed inan internal combustion engine combusting an ethanol-gasoline blend, saidmethod comprising combining the blend with at least one additiveselected from the group consisting of 2,6-di t-butyl phenol antioxidant,methylcyclopentadienyl manganese tricarbonyl combustion improver andoctane enhancer, oleic acid plus N,N dimethylcyclohexylarnine, dodecenylsuccinic acid, polyisobutylene amine dispersant, 1,2 propane diaminesalicylaldehyde metal deactivator, cresol Mannich base dispersant,diethanol amide of isostearic acid friction modifier, and 2-ethyl hexylnitrate combustion improver, whereby the deposits formed in said engineare less than the deposits formed in the engine when combusting theblend without the at least one additive.

In another example, a Keep Clean Test was performed by driving aChevrolet Impala for 5,000 miles using fuel containing gasoline withoutethanol, and fuel containing E85 blend. The Intake Valve Deposits (IVD)and the Combustion Chamber Deposits (CCD) were then measured and arereported in Table 3. The ethanol used in the E85 blend was ADM Ethanolexcept for Test No 6 where New Energy Ethanol was used.

TABLE 3 Keep Clean Test 5000 Miles IVD, CCD, Test No. Ethanol % H-6560,PTB mg mg 1 0 0 429 1232 2 0 85  5 1438 3 84  30/5(1) 191 299 4 7485/22(1) 134 265 5 84 0 227 184 6 84 0 99 176 7 84 500(2) 4 277 (1)Firstnumber is treat rate in the gasoline, second number is treat rate in thefinished blend. (2)H-6400 polyetheramine dispersant, not H-6560Table 3 illustrates the effect on deposits of having no ethanol (TestNo's 1 and 2) when used without and with (respectively) HiTEC® 6560, aMannich dispersant with a polyol and polyisobutylene carriers. The useof the Mannich dispersant reduced the IVD deposits from 429 mg to 5 mg.In the E85 fuel blend of Test No. 3 at a 5 PTB treat rate of the Mannichdispersant in the finished fuel had a IVD deposit of 191 mg but when thedispersant was lacking from the E85 blend (Test No. 5), the IVD depositwent up to 227, due in part to the contribution from the ethanol.Comparing Test No. 3 and Test No. 4 also shows that reducing the ethanolcontent in the fuel blend from 84% to 74% reduced the deposits from 299mg to 265 mg. This further illustrates that gasoline ethanol blends willneed better dispersancy and detergency. Test No. 6 used the New EnergyEthanol which as shown in Table 1 contributes much less to deposits thandoes the ADM Ethanol, so the IVD in Table 3 correspondingly shows only99 mg of deposit. Test No. 7 shows the result from a higher treat rate(500 PTB) of a polyetheramine dispersant instead of the Mannichdispersant and the result when combusting the E85 fuel was an amazinglylow 4 mg of deposit, at least a major portion of which can be attributedto the ethanol by comparing to Test No. 6.

For the CCD results of Table 3, comparing Test No. 3 (E85 plus Mannichdispersant) and Test No. 5 (E85 without the Mannich dispersant) one seesan improvement in reducing Combustion Chamber Deposits from 299 mg to184 mg and using the cleaner New Energy Ethanol of Test No. 6 reducedthe Combustion Chamber Deposit even further to 176 mg.

In this manner it is clear that the present disclosure provides a methodto reduce the Intake Valve Deposits and Combustion Chamber Deposits inan engine combusting an ethanol-containing fuel by adding to the fuel apolyetheramine dispersant or a Mannich dispersant. It is thereforeexpected that the combination thereof will have similar or even enhancedand synergistic results. The reduction of deposit formation is directlyrelated to reduction in engine wear.

TABLE 4 Treat Rate, Run BLEND PTB MWSD 1 E85 — 605 2 E85 + H4142 50 4453 E85 + 50% DDSA 25 540 4 E85 with ADM Ethanol — 495 H-6560 is a Mannichdispersant containing a PIB carrier and a polyol carrier E85 with ADMEthanol has the DCI-11 (@32PTB) corrosion ethanol MWSD is measured inmicrons.Table 4 shows the results of wear scar testing in which a median wearscar diameter MWSD) is reported. Run 1 was E85 using New Energy Ethanoland this baseline MWSD was 605. When HiTEC® 4142 (oleic acid plus N,Ndimethylcyclohexylamine) was added as a corrosion inhibitor, the MWSDwas reduced to 445. Changing the corrosion inhibitor in the E85 fuel toDDSA (50% in A150 solvent) gave a slightly higher value of 540 but stillimproved over the baseline for E85. Using ADM Ethanol in the E85produced even further reduction in the wear scar, probably due to thecorrosion inhibitor (DCI-11) in the ethanol. This Table shows thebenefit in wear scar reduction and hence in reducing wear in an engineachieved by incorporation of dodecenyl succinic acid and/or oleic acidplus N,N dimethylcyclohexylamine into an ethanol-containing gasolinefuel blend.

Other embodiments of the present disclosure will be apparent to thoseskilled in the art from consideration of the specification and practiceof the disclosure disclosed herein. As used throughout the specificationand claims, “a” and/or “an” may refer to one or more than one. Unlessotherwise indicated, all numbers expressing quantities of ingredients,properties such as molecular weight, percent, ratio, reactionconditions, and so forth used in the specification and claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the specification and claims are approximations that mayvary depending upon the desired properties sought to be obtained by thepresent disclosure. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should at least be construed in lightof the number of reported significant digits and by applying ordinaryrounding techniques. Notwithstanding that the numerical ranges andparameters setting forth the broad scope of the disclosure areapproximations, the numerical values set forth in the specific examplesare reported as precisely as possible. Any numerical value, however,inherently contains certain errors necessarily resulting from thestandard deviation found in their respective testing measurements. It isintended that the specification and examples be considered as exemplaryonly, with a true scope and spirit of the disclosure being indicated bythe following claims.

1. A method to reduce wear in an internal combustion engine, said methodcomprising combusting in said engine a fuel composition comprisinggasoline, ethanol and at least one fuel additive, said additive beingselected from the group consisting succinimide dispersants, succinamidedispersants, amides, Mannich base dispersants, and polyetheraminedispersants, whereby the engine wear is reduced relative to the enginewear when combusting a fuel composition without ethanol.
 2. The methodof claim 1, wherein the fuel composition comprises at least one secondfuel additive, said additive being selected from the group consisting ofphenolics, hindered phenolics, aryl amines, and diphenyl amines.
 3. Themethod of claim 1, wherein the fuel composition comprises at least onesecond fuel additive, said additive being selected from the groupconsisting of tall oil fatty acids, monocarboxylic acids, dicarboxylicacids, and polycarboxylic acids.
 4. The method of claim 1, wherein thefuel composition comprises at least one second fuel additive, saidadditive being selected from the group consisting of oxylatedalkylphenolic resins, and formaldehyde polymer with4-(1,1-dimethylethyl)phenol, methyloxirane and oxirane.
 5. The method ofclaim 1, wherein the fuel composition comprises at least one second fueladditive, said additive being selected from the group consisting ofmethyl cyclopentadienyl manganese tricarbonyl, cyclopentadienylmanganese tricarbonyl, azides, peroxides, and alkyl nitrates.
 6. Themethod of claim 1, wherein the fuel composition comprises at least onesecond fuel additive, said additive being selected from the groupconsisting of monoesters, diesters, ethers, diethers, polyethers, andglycols.
 7. The method of claim 1, wherein the fuel compositioncomprises at least one second fuel additive, said additive beingselected from the group consisting of p-phenylenediamine anddicyclohexylamine.
 8. The method of claim 1, wherein the fuelcomposition comprises at least one second fuel additive, said additivebeing selected from the group consisting of phenates, salicylates,sulfonates, nonylphenol ethoxylates, fuel-soluble alkali detergents andalkaline earth metal-containing detergents.
 9. The method of claim 1,wherein the fuel composition comprises at least one second fueladditive, said additive being selected from the group consisting ofmethyloxirane, oxiranes, peroxides, alkyl nitrates, C1—C8 aliphatichydrocarbons, ketones, butylene oxides, propylene oxides, ethyleneoxides, epoxides, butane, pentane, nitrous oxide, nitromethane, xylene,and diethyl ether.
 10. The method of claim 1, wherein the fuelcomposition comprises at least one second fuel additive, said additivebeing selected from the group consisting of tall oil fat acids,dodecenyl succinic acid, and oleic acid plus N,Ndimethylcyclohexylamine.
 11. A composition to improve wear protection inan internal combustion engine combusting an ethanol-containing fuel,said composition comprising gasoline, ethanol, and one or more materialsselected from the group consisting of succinimide dispersants,succinamide dispersants, amides, Mannich base dispersants,polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine,phenolics, hindered phenolics, aryl amines, diphenyl amines,monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methylcyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganesetricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolicresins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol,methyloxirane and oxirane, octane enhancer materials, monoesters,diesters, ethers, diethers, methyloxirane, oxiranes, peroxides, alkylnitrates, C1—C8 aliphatic hydrocarbons, ketones, butylene oxides,propylene oxides, ethylene oxides, epoxides, butane, pentane, nitrousoxide, nitromethane, xylene, diethyl ether, polyethers, glycols, alkalidetergents, phenates, salicylates, sulfonates, nonylphenol ethoxylates,and an alkaline earth metal-containing detergents.
 12. A method toreduce wear in an internal combustion engine combusting anethanol-containing fuel, said method comprising combusting in saidengine gasoline, ethanol, and one or more materials selected from thegroup consisting of succinimide dispersants, succinamide dispersants,amides, Mannich base dispersants, polyetheramine dispersants,p-phenylenediamine, dicyclohexylamine, phenolics, hindered phenolics,aryl amines, diphenyl amines, monocarboxylic acids, dicarboxylic acids,polycarboxylic acids, methyl cyclopentadienyl manganese tricarbonyl,cyclopentadienyl manganese tricarbonyl, azides, peroxides, alkylnitrates, oxylated alkylphenolic resins, formaldehyde polymer with4-(1,1 -dimethylethyl)phenol, methyloxirane and oxirane, octane enhancermaterials, monoesters, diesters, ethers, diethers, methyloxirane,oxiranes, peroxides, alkyl nitrates, C1—C8 aliphatic hydrocarbons,ketones, butylene oxides, propylene oxides, ethylene oxides, epoxides,butane, pentane, nitrous oxide, nitromethane, xylene, diethyl ether,polyethers, glycols, alkali detergents phenates, salicylates,sulfonates, nonylphenol ethoxylates, and alkaline earth metal-containingdetergents.
 13. A method to reduce deposit formation in an internalcombustion engine combusting an ethanol-containing fuel, said methodcomprising combusting in said engine gasoline, ethanol, and one or morematerials selected from the group consisting of succinimide dispersants,succinamide dispersants, amides, Mannich base dispersants,polyetheramine dispersants, p-phenylenediamine, dicyclohexylamine,phenolics, hindered phenolics, aryl amines, diphenyl amines,monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, methylcyclopentadienyl manganese tricarbonyl, cyclopentadienyl manganesetricarbonyl, azides, peroxides, alkyl nitrates, oxylated alkylphenolicresins, formaldehyde polymer with 4-(1,1-dimethylethyl)phenol,methyloxirane and oxirane, octane enhancer materials, monoesters,diesters, ethers, diethers, methyloxirane, oxiranes, peroxides, alkylnitrates, C1—C8 aliphatic hydrocarbons, ketones, butylene oxides,propylene oxides, ethylene oxides, epoxides, butane, pentane, nitrousoxide, nitromethane, xylene, diethyl ether, polyethers, glycols,phenates, salicylates, sulfonates, nonylphenol ethoxylates, alkalidetergents and alkaline earth metal-containing detergents.
 14. Themethod of claim 12, wherein the additive comprises a polyetheraminedispersant.
 15. A method to reduce wear in an internal combustionengine, said method comprising combusting in said engine a fuelcomposition comprising gasoline, ethanol and at least one fuel additive,said additive being selected from the group consisting of tall oil fattyacids, dodecenyl succinic acid, and oleic acid plus N,Ndimethylcyclohexylamine.
 16. A method of reducing deposits formed in aninternal combustion engine combusting an ethanol-gasoline blend, saidmethod comprising combining the blend with at least one additiveselected from the group consisting of 2,6-di t-butyl phenol,methylcyclopentadienyl manganese tricarbonyl, oleic acid plus N,Ndimethylcyclohexylamine, dodecenyl succinic acid, polyisobutylene aminedispersant, 1,2 propane diamine salicylaldehyde, cresol Mannich basedispersant, diethanol amide of isostearic acid, and 2-ethyl hexylnitrate, whereby the deposits formed in said engine are less than thedeposits formed in the engine when combusting the blend without the atleast one additive.
 17. The composition of claim 11, wherein thecomposition further comprises a fuel additive selected from the groupconsisting of lubricity additives, combustion improvers, detergents,dispersants, cold flow improvers, dehazers, demulsifiers, cetaneimprovers, antioxidants, scavengers, and pollution suppressants.
 18. Awear reducer fuel additive concentrate for gasoline engines combustingan ethanol-containing fuel, said concentrate comprising one or more wearreducing agents and a diluent selected from the group consisting of anoil, a fuel, gasoline, ethanol, solvent, carrier fluid, and other liquidmaterials combustible in a gasoline engine.
 19. A deposit reducer fueladditive concentrate for gasoline engines combusting anethanol-containing fuel, said concentrate comprising one or more depositreducing agents and a diluent selected from the group consisting of anoil, a fuel, gasoline, ethanol, solvent, carrier fluid, and other liquidmaterials combustible in a gasoline engine.